Keto-amido containing phenylazo benzothiazole dyestuffs

ABSTRACT

A benzothiazole azo dyestuff containing a benzene coupling component which, para to the azo bridge, is substituted by a secondary or tertiary amine group containing one or two N-bonded --C 2  H 4  --CO--NHC(CH 3 ) 2  CH 2  COCH 3  moieties. These dyestuffs are suitable for dyeing synthetic fibers.

This is a division of application Ser. No. 319,034, filed December 27,1972, issued on January 6, 1976 as U.S. Pat. No. 3,931,145.

This invention relates to dyes which are particularly useful in dyeingpolyester fibers, but which may also be employed to dye other syntheticmaterials such as acetate, triacetate, nylon, polyurethane, andpolyacrylonitrile.

Many dyes have been disclosed in the literature and have beenmanufactured which have certain desirable properties, but most if notall of them are lacking in some very important property.

For example, the dyes of U.S. Pat. No. 3,178,405, as exemplified by thedyestuff having the formula: ##STR1## are adversely affected in theirfastness properties, especially ozone fastness evidenced by shade changewhen subjected to durable press treatments, for example, the so-calledKorotron resin finish, requiring relatively high curing temperature.

Likewise, the dyes of US Pat. No. 3,268,507, as exemplified by thecompound having the formula: ##STR2## are similarly adversely affectedin their fastness properties, when subjected to durable press treatment.The dyes also have a slightly objectionable red flare under artificiallight.

A similar deficiency is found after durable press resin treatment in thedyes of US Pat. No. 3,406,165, as exemplified by the compound having theformula: ##STR3##

Typical fastness properties which are affected by durable presstreatment are light fastness, ozone fastness, shade change and fastnessto alkaline perspiration. In particular, a pronounced weakness infastness to alkaline perspiration is noted in those dyes included withinthe scope of US Pat. No. 3,406,165.

This same deficiency is also noted in dyes like those of formula (C)which have a terminal unsubstituted amide substituent, e.g. --NHC₂ H₄CONH₂. Dyestuffs containing such a terminal substituent are specificallydisclosed in US Pat. No. 2,346,013 and are subject to the samedeficiency. The latter patent also specifically discloses some dyescontaining a terminal substituted amidecontaining substituent differentfrom those of the present invention.

It is an object of this invention to provide a dye-stuff, and fibrousmaterial dyed therewith, which will not be subject to one or more of theabove deficiencies or disadvantages. Another object is the provision ofa novel compound suitable for use as the coupling component in such adyestuff. Other objects and advantages will appear as the descriptionproceeds.

We have now found a class of dyestuffs which have outstanding overallproperties. The dyes undergo durable press treatment, e.g. by theKorotron resin treatment, without obvious loss of fastness properties.That is, they withstand durable press resin treatment withoutobjectionable loss of light fastness, ozone fastness, shade change andfastness to perspiration. Furthermore the dyes of this type which arenavy in shade do not exhibit red flare, that property wherein a bluedyestuff becomes redder under artificial light. This objectionable redflare is especially noticeable with the dyes of US Pat. No. 3,406,165.Sublimation properties are likewise excellent with the dyes of thisinvention.

The attainment of the above objects is made possible by the presentinvention which includes the provision of a compound of the formula:##STR4## wherein Z is hydrogen, halo, lower alkyl, or NHX; X is SO₂ R,SO₂ OR, COR or COOR; R is hydrogen, lower alkyl or phenyl; Y ishydrogen, lower alkyl or lower alkoxy; R¹ is C₂ H₄ CONHC(CH₃)₂ CH₂ COCH₃; and R² is R¹ or lower alkyl, lower alkenyl or lower alkynyl optionallysubstituted by chlorine, bromine, fluorine, hydroxy, cyano, thiocyano,lower alkoxy, hydroxyethoxy, polyloweralkyleneoxy, lower alkoxycarbonyl,lower alkanoyloxy, benzoyloxy, or carbamyl optionally substituted byN-mono- or N,N-di-lower alkyl.

The attainment of the above objects is also made possible by theprovision of a dyestuff of the formula:

    D-- N═ N--Cp                                           (II)

wherein D is the radical of a diazo component, and Cp is a couplingcomponent of the formula defined in claim 1 coupled para to the --NR¹ R²group.

As employed herein, the term "lower" has reference to a moietycontaining about 1 to 4, and preferably 1 or 2, carbon atoms, whereby"alkyl" for example includes methyl, ethyl, propyl, and butyl, "alkenyl"includes allyl and ethenyl, and "alkynyl" includes propargyl andacetylene. It will be understood that the H atom in the above --NHXgroup may if desired be substituted by one of the R² substituents otherthan R¹, that R² may be substituted by a quaternary ammonium,pyrridinium, 2-pyrrolidinone, or phthaloylimino group or the like, andthat these dyestuffs, or the precursor coupling component, may bereadily quaternized by reaction with known alkylating agents such asbenzyl chloride, ethyl bromide, ethyl chloride, methyl iodide,dimethylsulfate, ethyl p-toluene sulfonate, and the like.

The compound of formula (I) above may be prepared by reacting a compoundof the formula: ##STR5## with one or two moles, optionally in each casewith up to 10% in excess thereof, of diacetone acrylamide of theformula: ##STR6## The reaction is generally conducted at elevatedtemperatures such as about 80° to 115° C. for about 15 to 72 hours,preferably in glacial acetic acid as solvent. To the resulting couplersolution (the acetic acid need not be removed) is added the diazo fromthe primary amine compound of the formula:

    D--NH.sub.2                                                (VI)

the coupling reaction and isolation of the desired dyestuff is carriedout in routine, known manner.

Alternatively, a compound of formula (III) or (IV) above may be firstcoupled with the diazo from the compound of formula (VI) above, and theresulting dyestuff then reacted with one or two moles of the compound offormula (V) above.

According to another method, a compound of the formula:

    Hal-C.sub.2 H.sub.4 CONHC(CH.sub.3).sub.2 CH.sub.2 COCH.sub.3 (VII)

wherein Hal is bromine or preferably chlorine, is reacted with acompound of formula (III) or (IV) above, preferably in the presence ofan acid binding agent, prior to or after the latter compound (III) or(IV) is coupled with the diazo from the compound of formula (VI).

Although any diazotizable primary aromatic amine compound of formula(VI) above may be employed in preparing the dyestuffs of this invention,a preferred type has the formula: ##STR7## wherein D¹ is hydrogen,chlorine, bromine, fluorine, cyano, thiocyano, lower alkylsulfonyl,trifluoromethyl, lower alkoxy, lower alkanoyl, benzoyl, loweralkoxycarbonyl, or carbamyl or sulfamyl optionally substituted byN-mono- or N,N-di-lower alkyl; and D² and D³ are individually hydrogen,nitro, or one of the D¹ substituents.

Another type of compound of formula (VI) which may be employed for theattainment of the desired results has the formula: ##STR8## wherein D⁴is hydrogen, halo, cyano, thiocyano, nitro, lower alkyl,loweralkylsulfonyl, trifluoromethyl, lower alkoxy, lower alkanoyl,benzoyl, lower alkoxycarbonyl, or carbamyl or sulfamyl optionallysubstituted by N-mono- or N,N-di-lower alkyl, and D⁵ is hydrogen, halo,lower alkoxy, lower alkyl, or nitro.

Examples of the diazo component of formula (VI) above which may beemployed in the production of these dyestuffs are as follows:

p-nitroaniline

2-chloro-4-nitroaniline

2,6-dichloro-4-nitroaniline

6-chloro-2,4-dinitroaniline

2-bromo-4-nitroaniline

2,6-dibromo-4-nitroaniline

2-bromo-4-nitroaniline

6-bromo-2,4-dinitroaniline

2-fluoro-4-nitroaniline

2,4,6-trichloroaniline

2-chloro-6-cyano-4nitroaniline

2-bromo-6-cyano-4-nitroaniline

2-cyano-4-nitroaniline

2-thiocyano-4-nitroaniline

2-nitro-4-thiocyanoaniline

2-methoxy-4-nitroaniline

2,4-di(trifluoromethyl)aniline

2-nitro-4-trifluoromethylaniline

4-nitro-2-trifluoromethylaniline

6-chloro-2-trifluoromethyl-4-nitroaniline

2,6-di(trifluoromethyl)-4-nitroaniline

2-methylsulfonyl-4-nitroaniline

2-ethylsulfonyl-4-nitroaniline

2-chloro-6-methylsulfonyl-4-nitroaniline

2-bromo-6-methylsulfonyl-4-nitroaniline

2,4-di(methylsulfonyl)aniline

6-chloro-2,4-di(methylsulfonyl)aniline

2-carboethoxy-4-nitroaniline

2-sulfamyl-4-nitroaniline

4-sulfamylaniline

2,4-dinitro-6-(dimethylsulfamyl)aniline

2,4-dinitro-6-ethylsulfamylaniline

2-amino-5-nitrobenzenesulfonic acid fluoride

p-aminoacetophenone

p-acetamidoaniline

2-aminobenzothiazole

2-amino-6-chlorobenzothiazole

2-amino-4,6-dichlorobenzothiazole

2-amino-5,6-dichlorobenzothiazole

2-amino-6-bromobenzothiazole

2-amino-6-fluorobenzothiazole

2-amino-6-cyanobenzothiazole

2-amino-6-thiocyanobenzothiazole

2-amino-6-nitrobenzothiazole

2-amino-4,6-dinitrobenzothiazole

2-amino-6-methylbenzothiazole

2-amino-4,6-dimethylbenzothiazole

2-amino-6-methoxybenzothiazole

2-amino-4,7-dimethoxybenzothiazole

2-amino-6-ethoxybenzothiazole

2-amino-5,6-diethoxybenzothiazole

2-amino-6-carboethoxybenzothiazole

2-amino-6-sulfamoylbenzothiazole

2-amino-6-(dimethylsulfamoyl)benzothiazole

2-amino-6-methylsulfonylbenzothiazole

2-amino-6-ethylsulfonylbenzothiazole

2-amino-6-acetylbenzothiazole

2-amino-6-benzoylbenzothiazole

Examples of the coupler precursor of formulas (III) or (IV) above whichare useful in the preparation of the compounds and dyestuffs of thisinvention are:

aniline

N-chloroethylaniline

N-hydroxyethylaniline

N-cyanoethylaniline

N-carbomethoxyethylaniline

N-carboethoxyethylaniline

N-ethoxyethylaniline

N-phenoxyethylaniline

N-benzyloxyethylaniline

N-methylcarbamoylethylaniline

N-ethylcarbamoylethylaniline

N-diethylcarbamoylethylaniline

N-(ethylcarbamoyloxyethyl)aniline

N-(dimethylcarbamoyloxyethyl)aniline

N-(phenylcarbamoyloxyethyl)aniline

N-(propoxycarbonylethyl)aniline

N-ethylcarbonyldioxyethylaniline

N-(3-chloro-2-hydroxypropyl)aniline

N-(3-chloro-2-acetoxypropyl)aniline

N-(chloroacetoxyethyl)aniline

m-chloroaniline

N-chloroethyl-m-chloroaniline

m-bromoaniline

N-bromoethyl-m-bromoaniline

o-toluidine

m-toluidine

N-ethyl-m-toluidine

N-cyanoethyl-m-toluidine

N-chloroethyl-m-toluidine

N-hydroxyethyl-m-toluidine

o-anisidine

N-methyl-o-anisidine

m-anisidine

N-methyl-m-anisidine

N-ethyl-m-anisidine

N-ethyl-o-phenetidine

m-aminoacetanilide

3'-(N-hydroxyethylamino)acetanilide

3'-(N-cyanoethylamino)acetanilide

3'-(N-ethoxyethylamino)acetanilide

3'-(ethylamino)acetanilide

3'-(ethylamino)benzanilide

3'-amino-4'-methoxyacetanilide

3'-amino-4' -ethoxyacetanilide

3'-(ethylamino)-4'-methoxyacetanilide

3'-(cyanoethylamino)-4'-methoxyacetanilide

3'-(hydroxyethylamino)-4'-methoxyacetanilide

3'-(methoxyethylamino)-4'-methoxyacetanilide

3'-(N-methylcarbamoylethylamino)-4'-methoxyacetanilide

3'-(N-ethylcarbamoyloxyethylamino)-4'-methoxyacetanilide

3'-(N-dimethylcarbamoyloxyethylamino)-4'-methoxyacetanilide

3'-(N-propoxycarbonylethylamino)-4'-methoxyacetanilide

3'-(N-ethylcarbonyldioxyethylamino)-4'-methoxyacetanilide

3'-(N-3-chloro-2-hydroxypropylamino)-4'-methoxyacetanilide

3'-(N-3-chloro-2-acetoxypropylamino)-4'-methoxyacetanilide pg,13

3'-(N-chloroacetoxyethylamino)-4'-methoxyacetanilide

3'-(ethylamino)-4'-ethoxyacetanilide

The dyestuffs of this invention are of the disperse type, beingsparingly to non-soluble in water, and are generally applied to fibrousmaterial by the disperse method with the aid of the known dispersingagents, wetting agents and/or thickeners and the like. The Thermosolmethod of dyeing is preferable, involving padding the fibrous materialwith an aqueous dispersion of the dyestuff at elevated temperatures ofabout 140°-190° F., squeezed to a liquor:fiber ratio of about 0.5-1.5:1,dried, and cured at the usual temperatures of for example about350°-450° F.

The fibrous material suitable for coloration with these dyestuffs may bein any form such as woven, knot or felt fabrics, staple, filament, yarn,tow, or skein or the like, and may have a basis of cellulose acetate ortriacetate, polyamide such as nylon 66, polyolefin such aspolypropylene, polyacrylonitrile, such as Orlon or modified versionsthereof, or other synthetic organic polymer, preferably polyester suchas Dacron polyethylene terephthalate, alone or admixed with naturalfibers such as cotton or other cellulose forms, silk, wool, or the like.

The following examples illustrate the invention and are not limitative.All parts and proportions referred to herein and in the appended claimsare by weight unless otherwise indicated.

EXAMPLE 1

Preparation of the coupling component having the formula: ##STR9##

38.8 g. (0.2 mole) 5-acetamido-o-phenetidide are dissolved in 100 ml.glacial acetic acid. 37 g. (0.22 mole) diacetone acrylamide are added.After solution in glacial acetic acid it is heated to 85° C. Thereaction is followed by thin layer chromatography (TLC). After 8 hoursat 85° C. about 80% of the starting free amine has been converted to themonosubstituted product. An additional 3.7 g. (10%) diacetone acrylamideare added. After another 8 hours at 85° C. about 90% of the product ismonosubstituted. Another 3.7 g. diacetone acrylamide are added. Afteranother 8 hours at 85° C. no free amine remains.

EXAMPLE 2

Preparation of the dyestuff having the formula: ##STR10##

The diazonium salt of 6-chloro-2,4-dinitroaniline is prepared in knownmanner by dissolving 21.7 g. (0.1 mole) in 105 g. sulfuric acid 66° Be.It is stirred 2 hours. To this is added slowly 0.1 mole nitrosylsulfuric acid (prepared by dissolving 6.9 g. sodium nitrile in 100 g.sulfuric acid 100%). The diazo is stirred 2 hours and then added slowly(dropwise) to a cold coupler solution consisting of one half thesolution of Example 1 to which has been added 20 ml. hydrochloric acid20° Be. and 600 ml. water. The pH is raised to 5-6 with sodium acetate.The precipitated product was filtered, washed with water and dried. 45.9g. (77%) of dyestuff are obtained. It dyes polyester a rich navy blue.

EXAMPLE 3

Preparation of a coupler product having the formula: ##STR11##

A diacetone acrylamide product is prepared as in Example 1. The aceticacid is neutralized with 70 ml. sodium hydroxide (30% by weight) to pH6. The amorphous material is dissolved in 250 ml. isopropanol and heatedto 85° C. 28 g. (0.22 mole) diethylsulfate is added slowly over a 2 hourperiod. A pH 5.0-6.0 is maintained by addition of barium carbonate. Thereaction is followed by TLC. Heating is continued at 85° C. for 72 hoursmaking 5 g. additions of diethyl sulfate approximately every 8 hours andmaintaining a pH of 5.0-6.0 with barium carbonate. At the end of thistime TLC shows that all of the monosubstituted product has beenconverted into a disubstituted product.

EXAMPLE 4

Preparation of the dyestuff having the formula: ##STR12##

In a manner similar to Example 2, 26.2 g. (0.1 mole)6-bromo-2,4-dinitroaniline are diazotized and coupled. The coupler isprepared by adding to one-half of the solution of Example 3 (0.1 mole),500 ml. water and 10 ml. hydrochloric acid 20° Be. and cooling in an icebath. The diazo is added dropwise over a 1 hour period. Sodium acetateis added near the end of the coupling to insure completeness of thereaction. The product is filtered, washed neutral and dried. 55.5 g drydyestuff are obtained (84%). It dyes polyester fiber a greenish-blueshade.

EXAMPLE 5

Preparation of the coupling component having the formula: ##STR13##

In the manner of Example 1, 72 g. (0.4 mole) 2-amino-4-acetanisidide aredissolved in 200 ml. glacial acetic acid along with 74 g. diacetoneacrylamide (0.44 mole). The reaction mix is heated at 85° C. for 24hours with 10% increment additions of diacetone acrylamide until TLCshows the free amine to have disappeared.

EXAMPLE 6

Preparation of the dyestuff having the formula: ##STR14##

13.8 g. (0.1 mole) p-nitroaniline are diazotized in known manner. Thisdiazo solution is added dropwise to a solution of the coupler preparedby dissolving 1/4 of the product of Example 5 (0.1 mole) in 25 ml.hydrochloric acid 20° Be. and 500 ml. water, and cooling in an ice bath.Sodium acetate is added to insure completeness of coupling. The productis filtered, washed neutral and dried. 33.7 g. (68%) dyestuff areobtained which dyes polyester deep red-violet shades.

EXAMPLE 7

Preparation of a coupling component having the formula: ##STR15##

In a manner similar to Example 1, 90 g. 3-amino-acetanilide (0.6 mole),as the HCl salt, are dissolved in 450 ml. glacial acetic acid. 50 g.sodium acetate are added. 111.6 g. diacetone acrylamide (0.66 mole) areadded and heated at 100° C. for 24 hours with 10% increment additions ofdiacetone acrylamide until TLC shows no free amine.

EXAMPLE 8

Preparation of the dyestuff having the formula: ##STR16##

24.2 g 2-Bromo-6-cyano-4-nitroaniline (0.1 mole) are diazotized usingnitrosyl sulfuric acid in the manner of Example 2. The diazo solution isadded to 1/6 the product of Example 7 (0.1 mole) which is dissolved in25 ml. hydrochloric acid 20° Be. and 500 ml. water cooled in an icebath. 32 g. product are obtained which dyes polyester fiber in mediumblue shades.

EXAMPLE 9

Preparation of the coupling component having the formula: ##STR17##

In a manner similar to Example 1, 127.5 g. m-chloroaniline (1.0 mole)are dissolved in 500 ml. glacial acetic acid. 185.9 g. diacetoneacrylamide are added and the charge heated at 100° C. for 24 hours. Noadditional diacetone acrylamide is necessary.

EXAMPLE 10

Preparation of the dyestuff having the formula: ##STR18##

In the manner of Example 2, 21.6 g. (0.1 mole)2-methylsulfonyl-4-nitroaniline are diazotized using nitrosyl sulfuricacid. This is added dropwise to 1/10 the product of Example 9 which hasbeen dissolved in 100 ml. glacial acetic acid, 200 ml. water, and cooledin an ice bath. After filtering, washing and drying, 25.6 g. (50%)product are obtained. The product dyes polyester in reddish-brownshades.

EXAMPLE 11

Preparation of the coupling component having the formula: ##STR19##

In the manner of Example 1, 146 g. N-cyanoethylaniline (1.0 mole), 500ml. glacial acetic acid and 169 g. diacetone acrylamide are heatedtogether at 100° C. for 24 hours with 10% diacetone acrylamideincrements added until TLC shows disappearance of free amine.

EXAMPLE 12

Preparation of a dyestuff having the formula: ##STR20##

In the manner of Example 2, 20.7 g. 2,6-dichloro-4-nitroaniline (0.1mole) are diazotized with nitrosyl sulfuric acid, and added dropwise toa cold solution of 1/10 Example 11 (0.1 mole) dissolved in 300 ml.water. After filtering, washing and drying 35 g. product (66%) areobtained which dyes polyester fiber in yellow-brown shades.

EXAMPLE 13

Preparation of the dyestuff having the formula: ##STR21##

A hot (95° C.) solution 19.5 g. 2-amino-6-nitrobenzothiazole (0.1 mole)in 400 ml. glacial acetic acid is added dropwise to a mixture of 120 g.glacial acetic acid and 100 g. nitrosyl sulfuric acid at 15°-20° C. Themass is stirred 11/2 hours. This dark orange diazo solution is addedslowly over a one-half hour period to a solution equivalent to theglacial acetic acid solution of 0.1 mole of the coupler of Example 1.This mixture is stirred in an ice bath 2 hours, and then drowned into 5l. ice and water to yield 38 g. product (67%). The product dyespolyester fiber bright violet shades.

EXAMPLE 14

Preparation of the dyestuff having the formula: ##STR22##

In the manner of Example 13, 21.9 g. 5,6-dichloro-2-aminobenzothiazole(0.1 mole) are added to 400 ml. glacial acetic acid and diazotized withnitorsyl sulfuric acid. This is added slowly to a cold solution of 0.1mole coupler of Example 7 to yield 38 g. (69%) of a product which dyespolyester fiber a bright red shade.

The dye components shown in the following table are reacted in a mannersimilar to the above to produce dyestuffs and results in accordance withthis invention, as indicated.

                                      TABLE                                       __________________________________________________________________________    Ex.                                                                              Diazo Base         Coupler                 Shade                           __________________________________________________________________________    15 2-Chloro-4-nitroaniline                                                                           ##STR23##              Red                             16 2-Cyano-4-nitroaniline                                                                           "                       Rubine                          17 Sulfanilamide      "                       Orange                          18 2-Methylsulfonyl-4-nitroaniline                                                                  "                       Pink                            19 2-Bromo-6-cyano-4-nitroaniline                                                                    ##STR24##              Salmon                          20 2-Chloro-4,6-dinitroaniline                                                                       ##STR25##                                              21 2-Cyano-4-nitroaniline                                                                           "                       Red Violet                      22 2-Chloro-4,6-dinitroaniline                                                                       ##STR26##              Blue                            23 2-Bromo-4,6-dinitroaniline                                                                       "                       Blue                            24 2,6-Dichloro-4-nitroaniline                                                                      "                       Gray Violet                     25 2-Bromo-4,6-dinitroaniline                                                                       "                       Blue                            26 2-Bromo-6-cyano-4-nitroaniline                                                                   "                       Greenish Blue                   27 p-nitroaniline     "                       Red Violet                      28 2-chloro-4-nitroaniline                                                                          "                       Violet                          29 p-nitroaniline                                                                                    ##STR27##              Orange                          30 p-aminoacetophenone                                                                              "                       Yellow                          31 2-Chloro-4-nitroaniline                                                                          "                       Red Orange                      32 2-Trifluoromethyl-4-nitroaniline                                                                 "                       Red                             33 p-nitroaniline                                                                                    ##STR28##              Orange                          34 2-Chloro-4-nitroaniline                                                                          "                       Red Orange                      35 2-Cyano-4-nitroaniline                                                                           "                       Red                             36 2-Chloro-4,6-dinitroaniline                                                                      "                       Violet                          37 p-cyanoaniline     "                       Orange                          38 2-Chloro-4-nitroaniline                                                                           ##STR29##              Rubine                          39 2,6-Dichloro-4-nitroaniline                                                                      "                       Red Brown                       40 2-Bromo-6-cyano-4-nitroaniline                                                                   "                       Blue Violet                     41 2-Amino-5,6-dichlorobenzothiazole                                                                 ##STR30##              Pink                            42 2-Amino-6-nitrobenzothiazole                                                                     "                       Violet                          43 2-Amino-5,6-dichlorobenzothiazole                                                                 ##STR31##              Blue Violet                     44 2-Amino-6-ethoxybenzothiazole                                                                    "                       Blue Violet                     45 2-Amino-5,6-dichlorobenzothiazole                                                                 ##STR32##              Pink                            46 2-Amino-6-chlorobenzothiazole                                                                    "                       Violet                          47 2-Amino-6-chlorobenzothiazole                                                                     ##STR33##              Orange                          48 2-Amino-6-nitrobenzothiazole                                                                     "                       Red Violet                      49 2-Chloro-4-nitroaniline                                                                           ##STR34##              Red Orange                      50 2-Cyano-4-nitroaniline                                                                           "                       Red Orange                      51 2,6-Dichloro-4-nitroaniline                                                                      "                       Red Brown                       52 2-Amino-5,6-dichlorobenzothiazole                                                                "                       Red                             53 2-Chloro-4-nitroaniline                                                                           ##STR35##              Red                             __________________________________________________________________________

EXAMPLE 54

The dyestuff of Example 2 is dispersed to a 13% active paste in a VibroEnergy Mill using Tamol SN (sodium salt of condensed naphthalenesulfonicacid, Rohm and Hass Co.) and Marasperse CB (partially desulfonatedsodium lignosulfonate, Am. Can Co.).

About 2 oz. of this dispersed dyestuff are dispersed in 83 cc. warmwater and poured into a solution containing 0.2 g. Keltex gum (alginicthickening agent), and 1 cc. Nekal NF (sodium alkylnaphthalenesulfonate,GAF Corp.). This dispersion or solution is made up to a gallon withwater.

Dacron polyester material is padded with the above dyebath at 160° F.,dried and cured at 425° F. for 90 seconds. The material is soaped at theboil for 5 minutes, washed and dried. A rich navy blue coloration isobtained which has excellent light fastness. After Korotron permanentpress treatment, the dyeings maintain excellent light fastness, no shadechange and excellent fastness of alkaline and acid perspiration. Anotheradvantage is lack of red flare under artificial light.

This invention has been disclosed with respect to certain preferredembodiments, and it will be understood that modifications and variationsthereof will become obvious to persons skilled in the art and areintended to be included within the spirit and purview of thisapplication and the scope of the appended claims.

We claim:
 1. A dyestuff of the formula: ##STR36## wherein D⁴ ishydrogen, chlorine, bromine, fluorine, cyano, thiocyano, nitro, loweralkyl, lower alkylsulfonyl, trifluoromethyl, lower alkoxy, loweralkanoyl, benzoyl, lower alkoxycarbonyl, or carbamyl or sulfamyloptionally substituted by N-mono- or N,N-di-lower alkyl;D⁵ is hydrogen,chlorine, bromine, fluorine, lower alkoxy, lower alkyl, or nitro; Z ishydrogen, halogen, lower alkyl or NHX and X is SO₂ --R, SO₂ OR, COR orCOOR with R being hydrogen, phenyl or lower alkyl; Y is hydrogen, loweralkyl or lower alkoxy; R² is --C₂ H₄ --CO--NHC(CH₃)₂ CH₂ COCH₃,hydrogen, lower alkyl, lower alkenyl, lower alkynyl; or lower alkyl,lower alkenyl or lower alkynyl substituted with chlorine, bromine,fluorine, hydroxy, cyano, thiocyano, lower alkoxy, hydroxyethoxy, loweralkoxycarbonyl, lower alkanoyloxy, benzoyloxy, unsubstituted carbamyl,N-mono-lower alkylcarbamyl, or N,N-di-lower alkylcarbamyl.
 2. A compoundas defined in claim 1 wherein R₂ is --C₂ H₄ --CO--NHC(CH₃)₂ CH₂ COCH₃.3. A dyestuff as defined in claim 1 having the formula: ##STR37##
 4. Adyestuff as defined in claim 1 having the formula: ##STR38##
 5. Fibrousmaterial colored with a dyestuff as defined in claim
 1. 6. Polyestermaterial colored with a dyestuff as defined in claim 1.